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CuN6(Br)2 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight hydrobromic acid molecules and one CuN6 framework. In the CuN6 framework, Cu2+ is bonded in an octahedral geometry to six equivalent N2- atoms. All Cu–N bond lengths are 2.81 Å. N2- is bonded in a 5-coordinate geometry to one Cu2+ and four equivalent N2- atoms. All N–N bond lengths are 1.72 Å.
CuN6(Br)2 crystallizes in the tetragonal I4/mmm space group. The structure is one-dimensional and consists of four hydrobromic acid molecules and two CuN6 ribbons oriented in the (0, 0, 1) direction. In each CuN6 ribbon, Cu2+ is bonded in a linear geometry to two equivalent N2- atoms. Both Cu–N bond lengths are 1.83 Å. There are two inequivalent N2- sites. In the first N2- site, N2- is bonded in a distorted single-bond geometry to one Cu2+ and four equivalent N2- atoms. All N–N bond lengths are 1.65 Å. In the second N2- site, N2- is bonded in a 4-coordinate geometry to four N2- atoms. Both N–N bond lengths are 1.83 Å.